The Fe 2 (NO) 2 Diamond Core: A Unique Structural Motif In Non‐Heme Iron–NO Chemistry
| Autor: | Debangsu Sil, Hai T. Dong, Claire E. Kozemchak, Amy L. Speelman, Carsten Krebs, Nicolai Lehnert |
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| Rok vydání: | 2019 |
| Předmět: |
Spin states
010405 organic chemistry Dimer Diamond Disproportionation Bioinorganic chemistry General Medicine General Chemistry engineering.material Type (model theory) 010402 general chemistry 01 natural sciences Catalysis 0104 chemical sciences chemistry.chemical_compound Crystallography chemistry engineering Non heme iron Structural motif |
| Zdroj: | Angewandte Chemie International Edition. 58:17695-17699 |
| ISSN: | 1521-3773 1433-7851 |
| DOI: | 10.1002/anie.201911968 |
| Popis: | Non-heme high-spin (hs) {FeNO}8 complexes have been proposed as important intermediates towards N2 O formation in flavodiiron NO reductases (FNORs). Many hs-{FeNO}8 complexes disproportionate by forming dinitrosyl iron complexes (DNICs), but the mechanism of this reaction is not understood. While investigating this process, we isolated a new type of non-heme iron nitrosyl complex that is stabilized by an unexpected spin-state change. Upon reduction of the hs-{FeNO}7 complex, [Fe(TPA)(NO)(OTf)](OTf) (1), the N-O stretching band vanishes, but no sign of DNIC or N2 O formation is observed. Instead, the dimer, [Fe2 (TPA)2 (NO)2 ](OTf)2 (2) could be isolated and structurally characterized. We propose that 2 is formed from dimerization of the hs-{FeNO}8 intermediate, followed by a spin state change of the iron centers to low-spin (ls), and speculate that 2 models intermediates in hs-{FeNO}8 complexes that precede the disproportionation reaction. |
| Databáze: | OpenAIRE |
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